CN108137332A - The purposes of molecular sieve SSZ-91, the method for preparing SSZ-91 and SSZ-91 - Google Patents

The purposes of molecular sieve SSZ-91, the method for preparing SSZ-91 and SSZ-91 Download PDF

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CN108137332A
CN108137332A CN201680055395.2A CN201680055395A CN108137332A CN 108137332 A CN108137332 A CN 108137332A CN 201680055395 A CN201680055395 A CN 201680055395A CN 108137332 A CN108137332 A CN 108137332A
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molecular sieve
ssz
reaction mixture
zsm
polytype
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A·F·奥乔
谢丹
张义华
雷光韬
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Chevron USA Inc
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Chevron USA Inc
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Priority claimed from US14/837,071 external-priority patent/US9802830B2/en
Priority claimed from US14/837,108 external-priority patent/US9920260B2/en
Priority claimed from US14/837,094 external-priority patent/US20170056870A1/en
Priority claimed from US14/837,087 external-priority patent/US20170056869A1/en
Application filed by Chevron USA Inc filed Critical Chevron USA Inc
Publication of CN108137332A publication Critical patent/CN108137332A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7023—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/703—MRE-type, e.g. ZSM-48
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7446—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7461—MRE-type, e.g. ZSM-48
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B01J35/30—
    • B01J35/40—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Abstract

Family is disclosed to be named as the new crystalline molecular sieve of SSZ 91 and manufacture the method for SSZ 91 and the purposes of SSZ 91.Molecular sieve SSZ 91 is structurally similar to fall into the sieve in 48 molecular sieve races of ZSM, it is characterised in that：(1) there is the defects of low degree；(2) inhibit the low aspect ratio being hydrocracked, compared with ZSM 48 material of the conventional aspect ratio more than 8；(3) it is substantially pure phase.

Description

The purposes of molecular sieve SSZ-91, the method for preparing SSZ-91 and SSZ-91
Cross reference to related applications
This application involves the U.S. Patent Application No. 14/837,071 all submitted for 27th in August in 2015,14/837,087, It 14/837,094 and 14/837, No. 108, is incorporated by herein.
Technical field
New race this document describes the referred to as crystalline molecular sieve of SSZ-91 prepares the method for SSZ-91 and the use of SSZ-91 On the way.
Background of invention
Due to their unique screening characteristics and their catalytic performance, crystalline molecular sieve and molecular sieve are used especially for In such as application of hydrocarbon conversion, gas dry and separation.Although it is disclosed that many different crystalline molecular sieves, but still need To have for gas separation and the recruit of dry, hydrocarbon and the expected performance of chemical conversion and other application sieve.New point Son sieve may contain novel internal pore structure, provide the selectivity of enhancing in these methods.
Molecular sieve has different crystal structures, is confirmed by different X-ray diffractograms.Crystal structure defines difference The distinctive hole of classification and hole.
Molecular sieve is classified according to the rule of the IUPAC Zeolite Nomenclatures committee by the structure committee of International Zeolite Association.According to The classification, the framework-type zeolite and other crystalline microporous moleculars sieve for having been set up structure are assigned three-letter codes and retouch It is set forth in " Atlas of Zeolite Framework Types " the 6th revised edition, Elsevier (2007) and International Zeolite Association Molecular sieve structure database (http on website://www.iza-online.org).
It is that the structure of molecular sieve can be ordered into or unordered.Molecular sieve with ordered structure is in all three-dimensionals The Periodic Building Unit (PerBUs) of periodic arrangement.Structural disorder structure is shown less than three-dimensional periodic arrangement (that is, two Dimension, one-dimensional or zero dimension).When PerBUs is connected in different ways or when two or more PerBUs in same crystal altogether When raw, occur unordered.If realizing periodic arrangement in all three dimensions, claimed by the PerBUs crystal structures built For end member structure.
There is plane stacking defect defect in the case where material is in two dimensions containing sequence in disordered material (faults).Planar disfigurement defect has upset the channel of material pore system formation.Planar disfigurement defect near surface Diffusion path is limited, these diffusion paths are that the catalytical active part of raw material components access aperture system is allowed to need originally.Cause This, with the increase of defect level, the catalytic activity of material usually reduces.
In the case of the crystal with planar disfigurement, the explanation of X-ray diffractogram needs to simulate stacking disorder effect Ability.DIFFaX is the computer program based on mathematical model, for calculating the intensity of the crystal containing planar disfigurement.(referring to M.M.J.Treacy et al., Proceedings of the Royal Chemical Society, London, A (1991), the Volume 433, the 499-520 pages).DIFFaX is by International Zeolite Association's selection and can sieve coexisting phase from the model molecule that it is obtained XRD coatings simulation program is (referring to " Collection of Simulated XRD Powder Patterns for Zeolites ", M.M.J.Treacy and J.B.Higgins, 2001, fourth edition represents the structure committee of International Zeolite Association and goes out Version).If K.P.Lillerud et al. is at " Studies in Surface Science and Catalysis ", 1994, Volume 84, the 543-550 pages report, it is also used for the coexisting phase of theoretical research AEI, CHA and KFI molecular sieve.DIFFaX is A kind of method for disordered crystalline material (such as coexisting molecular sieve) the well-known establishment of characterization with planar disfigurement.
Title ZSM-48 refers to family's disordered material, each is characterized as having one-dimensional 10- tubular rings hole system.It is described Hole is formed by the cellular thin slice rolled for condensing 6 ring structure of tetrahedron, and hole includes 10 Tetrahedral atoms.Zeolite EU-2, ZSM-30 and EU-11 belong to ZSM-48 zeolites race.
According to Lobo and Koningsveld, ZSM-48 molecular sieves race is made of nine kinds of polytypes.(referring to J.Am.Chem.Soc.2002,124,13222-13230).These materials have closely similar but different X-ray diffraction Figure.Lobo and Koningsveld papers describe them and the Alexander Kuperman of Chevron Corporation are won The analysis for three kinds of ZSM-48 samples that scholar provides.Each being respectively labeled as in three kinds of samples of sample A, B and C uses three It is prepared by the different structure directing agent of kind.Following comparative example 2 and 3 corresponds to described in Lobo and Koningsveld papers Sample A and B.
Sample A is described as polytype 6 by Lobo and Koningsveld papers, and sample B is described as to the polytype 6 of defect. The paper further describes the form of sample A, is made of a diameter of about 20nm and the length acicular crystal for being about 0.5 micron. The long and narrow crystal that the form of sample B is about 0.5 μm by width and length is 4-8 μm forms.Such as following 2 and 3 institute of comparative example Show, the scanning electron microscope image of sample A and B are presented in this paper Fig. 3 and 4.
Kirschhock and its partner describe pure phase polytype 6 successful synthesis (referring to Chem.Mater.2009, 21,371-380).In their paper, (they are known as by its 6 material of pure phase polytype by Kirschhock and its partner COK-8) it is described as that there is very big length-width ratio (width 15-80nm, 0.5-4 μm of length), is grown along the hole direction of interconnection Long acicular crystal composition form.
As described in Kirschhock papers, pore structure is tieed up by 10 rings 1 from ZSM-48 family molecular sieves and formed, wherein by mutual The channel that the hole of connection is formed extends perpendicular to the long axis of needle.Therefore, access portal is located at the short end of needle.With these needles Length diameter ratio (also referred to as aspect ratio) increases, and the diffusion path of hydrocarbon charging also increases.With the increase of diffusion path, feed Residence time in channel also increases.The longer residence time causes the undesirable of charging to be hydrocracked increase, while adjoint The reduction of selectivity.
Therefore, it needs to show the ZSM-48 molecular sieve lower than known ZSM-48 molecular sieve hydrocrackings degree at present.Also it holds It is continuous need pure phase or substantially pure phase and in structure unordered (the defects of low degree) with low degree ZSM-48 Molecular sieve.
Brief summary of the invention
Described hereafter is a kind of crystalline molecular sieve races with unique properties, are referred to herein as " molecular sieve SSZ-91 " Or referred to as " SSZ-91 ".Molecular sieve SSZ-91 is structurally similar to fall into the molecular sieve of ZSM-48 races, it is characterised in that： (1) there is the defects of low degree；(2) inhibit the low aspect ratio being hydrocracked, 8 traditional ZSM-48 materials phase is more than with aspect ratio Than；And (3) are substantially pure phase.
As that will show in the following embodiments, three kinds of unique combination features for lacking SSZ-91 are (low aspect ratio, low The composition of EU-1 contents, high polytype 6) any one of ZSM-48 materials will show the catalytic performance gone on business.
On the one hand, the molecular sieve that silica is 40 to 200 to the molar ratio of aluminium oxide is provided.The X ray of this table 2 spreads out The ray representation SSZ-91 under intact form after its preparation.
It is such as simulated by DIFFaX and such as by Lobo and Koningsveld in J.Am.Chem.Soc.2012,124, Described in 13222-13230 determine, SSZ-91 materials by based on the whole ZSM-48 section bars material meters being present in product at least 70% polytype 6 forms, wherein unordered adjusted by probability the defects of three kinds of differences.It should be noted that phrase is " at least 70% " including in structure be not present other ZSM-48 polytypes (i.e. the material be 100% pure phase polytype 6) situation.
On the other hand, SSZ-91 is substantially pure phase.SSZ-91 contains other EUO type molecular sieve phases, in an amount of from total The 0-3.5% of product weight (including end value).
Molecular sieve SSZ-91 has the form for being characterized as polycrystalline aggregate, and each aggregation is characterized in that by totally having Crystallite composition of the average aspect ratio between 1 and 8 (including end values).Compared with the ZSM-48 materials with high aspect ratio, SSZ-91 shows being hydrocracked for lower degree.Aspect ratio 1 is ideal minimum, and length and width is identical.
On the other hand, a kind of method for preparing crystalline material is provided, by being contacted under crystallization condition：(1) at least one Kind silica source；(2) at least one alumina source；(3) source of at least one element selected from periodic table the 1st and 2 races；(4) hydrogen Oxygen radical ion；(5) hexamethonium C6 cation.
On the other hand, a kind of crystalline material of x-ray diffraction line of original sample state after preparation with table 2 is provided Method passes through：
(a) reaction mixture is prepared, the reaction mixture contains：(1) at least one silica source；(2) it is at least one Alumina source；(3) source of at least one element selected from periodic table the 1st and 2 races；(4) hydroxide ion；(5) hexamethonium C6 sun Ion；(6) water；With
(b) reaction mixture is maintained at and be enough under the crystallization condition to form molecular sieve crystal.
The brief description of accompanying drawing
Fig. 1 is powder x-ray diffraction (XRD) figure of the molecular sieve of original sample after the synthesis prepared in comparative example 1.
Fig. 2 is the scanning electron micrograph of the molecular sieve of original sample after the synthesis prepared in comparative example 1.
Fig. 3 is the scanning electron micrograph of the molecular sieve of original sample after the synthesis prepared in comparative example 2
Fig. 4 is the scanning electron micrograph of the molecular sieve of original sample after the synthesis prepared in comparative example 3.
Fig. 5 is the powder xrd pattern of the molecular sieve SSZ-91 of original sample after the synthesis prepared in embodiment 7.
Fig. 6 is the scanning electron micrograph of the molecular sieve SSZ-91 of original sample after the synthesis prepared in embodiment 7.
Fig. 7 is the scanning electron micrograph of the molecular sieve of original sample after the synthesis prepared in embodiment 8.
Fig. 8 is the simulation XRD of several DIFFaX generations of the molecular sieve SSZ-91 of original sample after the synthesis prepared in embodiment 8 Figure and powder xrd pattern.
Fig. 9 be several DIFFaX generations of the molecular sieve of original sample after the synthesis prepared in embodiment 11 simulation XRD diagram and Powder xrd pattern.
Figure 10 is the simulation XRD diagram and powder for several DIFFaX generations for comparing the molecular sieve of original sample after the synthesis prepared in 1 Last XRD diagram.
Figure 11 is the scanning electron micrograph of the molecular sieve of original sample after the synthesis prepared in embodiment 13.
Figure 12 be several DIFFaX generations of the molecular sieve of original sample after the synthesis prepared in embodiment 13 simulation XRD diagram and Powder xrd pattern.
It is described in detail
Brief introduction
Term " activated source " refers to reagent or precursor material, can be can react and can be incorporated into molecular sieve structure In at least one element of form supply.Term " source " and " active source " may be used interchangeably herein.
Term " molecular sieve " and " zeolite " are synonyms, and including (a) intermediate and (b) be final or target molecule sieve and Pass through (1) the directly molecular sieve of synthesis or (2) crystallization post processing (twice-modified).Secondary synthesis technology allows through hetero atom crystalline substance Lattice replace or other technologies synthesize target material by intermediary material.For example, alumino-silicate can be led to by intermediate borosilicate Al is replaced B and synthesized by heteroatom lattice substitution after crossing crystallization.This technology is known, such as September in 2004 is awarded on the 14th It gives described in the U.S. Patent No. 6,790,433 of C.Y. and Chen and Stacey Zones.
Term " * MRE- types molecular sieve " and " EUO- types molecular sieve " are including by all molecules of International Zeolite Association's name Sieve and its isotype skeleton, such as Atlas of Zeolite Framework Types, eds.Ch.Baerlocher, L.B.McCusker and D.H.Olson, Elsevier, the 6th revised edition, 2007 and International Zeolite Association website (http:// Www.iza-online.org described in the zeolite structured database on).
Term " periodic table " refers to the version of the IUPAC periodic table of elements on June 22nd, 2007, and the volume of periodic table race Number scheme such as Chem.Eng.News, 63 (5), 26-27 (1985) are described.
For the purpose of this specification and the appended claims, unless otherwise specified, will in specification and right The number and other numerical value for asking all expression quantity, percentage or the ratio that are used in book are interpreted as in all cases all It is modified by term " about ".Therefore, unless the contrary indication, otherwise proposed in following specification and appended book Numerical parameter is approximation, can be changed according to the desirable properties for wishing to obtain.Note that such as this specification and appended right Used in it is required that, singulative " one ", "one" and " described " include plural, except being limited to non-clearly and clearly one A instruction object.As it is used herein, term " comprising " and its grammatical variants are intended to be non-limiting so that in list The narration of project is not other similar items for excluding to replace or be added to Listed Items.As it is used herein, term "comprising" is meant to include within identified element or step after the term, but any such element or step is not poor Most, and embodiment can include other element or step.
Unless otherwise specified, the element of the cited mixture that can select single component or component, material or Other components, it is intended to be combined including the component listed and its all possible subgenus of mixture.It is in addition, given here all Digital scope all includes their upper and lower bound value.
The scope of the claims is defined by the claims, and can include the other embodiment that those skilled in the art expect.Such as These other embodiments of fruit have the not structural detail different from the literal language of claim or if they include and power Equivalent structural elements of the literal language without substantive difference of profit requirement, then these other embodiments intention is in the scope of the claims It is interior.With in reconcilable degree herein, all quotations cited herein are both incorporated herein by reference.
Reaction mixture and crystallization
When preparing SSZ-91, organising from ZSM-48 zeolites race's synthesis of molecular sieve is alternatively used for by least one It closes object and is used as structure directing agent (" SDA "), also referred to as crystallize template.For manufacturing the SDA of SSZ-91 by with lower structure (1) table Show：
N, N, N, N ', N ', N '-hexamethyl hexa-methylene diammonium or hexamethonium C6 cation
SDA cations usually and anionic associative, anion can be molecular sieve formation is not adversely affected it is any Anion.The representative example of anion includes hydroxide ion, acetate ion, sulfate ion, Carboxylic Acid Ions and halogen Ion, such as fluorine ion, chlorion, bromide ion and iodide ion.In one embodiment, anion is bromide ion.
In general, SSZ-91 is prepared by following steps：
(a) reaction mixture is prepared, the reaction mixture contains：(1) at least one silica source；(2) it is at least one Alumina source；(3) source of at least one element selected from the periodic table of elements the 1st and 2 races；(4) hydroxide ion；(5) pregnancy is double Ammonium cation；(6) water；(b) reaction mixture is maintained at and be enough under the crystallization condition to form molecular sieve crystal.
The reaction mixture for forming molecular sieve is as shown in table 1 below with forming for molar ratio computing：
Table 1
Wherein,
(1) M is selected from periodic table the 1st and the element of 2 races；With
(2) Q is the structure directing agent represented by structure 1 above.
Available for this paper silicon source include pyrogenic silica, precipitated silica, silica hydrogel, silicic acid, Colloidal silicon dioxide, orthosilicic acid tetraalkyl ester (such as tetraethyl orthosilicate) and silica hydroxides.
Silicon source available for this paper includes aluminate, aluminium oxide and aluminium compound, such as AlCl3、Al2(SO4)3、Al (OH)3, kaolin and other zeolites.The example of alumina source is LZ-210 zeolites (a kind of y-type zeolite).
As described previously for each embodiment as described herein, reaction mixture can be formed as containing at least one The source of element selected from periodic table the 1st and 2 races (herein referred as M).In a sub- embodiment, reaction mixture uses element The source of the 1st race's element of periodic table is formed.In another sub- embodiment, reaction mixture is formed using sodium (Na) source.It is any All will not be suitable to the compound containing M that crystallization process is harmful to.The source of this 1st and 2 race's element includes its oxide, hydrogen Oxide, nitrate, sulfate, halide, oxalates, citrate and acetate.
For each embodiment as described herein, molecular sieve reaction mixture can be supplied by more than one source.And And two or more reactive components can be provided by a kind of source.
Reaction mixture can be prepared in batches or continuously.When the crystalline size of molecular sieve described herein, form and crystallization Between can change with the property and crystallization condition of reaction mixture.
Reaction mixture is kept at elevated temperatures until forming molecular sieve crystal.In general, zeolite hydrothermal crystallization leads to It often carries out under stress and is usually performed such that reaction mixture is subjected to self-generated pressure and optionally stirs in autoclave, Keep for 1 to the time more than 18 hours at a temperature of between 125 DEG C and 200 DEG C.
As described above, SSZ-91 is the material of substantially pure phase.As used herein, term " basic phase pure material " refers to institute It states material and zeolite phase is entirely free of other than belonging to those zeolites of ZSM-48 races zeolite or with the selectivity for material Have the shortcomings that the amount than measurable smaller influence or imparting material smaller exists.It is common with two of SSZ-91 cocrystallization It is mutually EUO type molecular sieve such as EU-1 and Magadiite and Kenyaite.These other can mutually be used as individually mutually are deposited Or can be with SSZ-91 phase symbiosis.As the following examples are proved, there are a large amount of EU-1 to SSZ-91 in product The selectivity of hydroisomerization is harmful.
In one embodiment, SSZ-91 products contain other EUO type molecular sieve phases of 0-3.5 weight %.One In a sub- embodiment, SSZ-91 contains the EU-1 of 0.1 to 2 weight %.In another sub- embodiment, SSZ-91 contains The EU-1 of 0.1-1 weight %.
The ratio of known powder XRD peak intensities linearly becomes as the function of the weight fraction of two-phase arbitrary in mixture Change：(I α/I β)=(RIR α/RIR β) * (x α/x β), wherein RIR (referenced strength ratio) parameter can be in The International Centre for Diffraction Data's Powder Diffraction File (PDF) data Library (http://www.icdd.com/products/) in find.Therefore the weight percent of EUO phases is by measuring EUO phases Ratio between peak intensity and the peak intensity of SSZ-91 phases calculates.
Inhibit the formation of a certain amount of EUO phases, the temperature by selecting best hydrogel composition, temperature and crystallization time The formation for making EUO phases with crystallization time minimizes, while maximizes SSZ-91 products collection efficiencies.Following example is these processes The formation how variation of variable minimizes EU-1 provides guidance.Has the zeolite manufacturer of ordinary skill easily Can select to make EU-1 formation minimize needed for process variable because these variables will depend on production-scale size, Acceptable EU-1 material horizontals in the ability of available devices, desired target output and product.
During hydrothermal crystallization step, molecular sieve crystal can be made spontaneously to be nucleated from reaction mixture.Use molecular sieve Crystal can advantageously reduce the time completed needed for crystallization generation as seed crystal material.In addition, inoculation can be by promoting to divide The nucleation and/or form over any undesirable phase and the purity of the product obtained is caused to increase that son sieves.It has been found, however, that If using inoculation, seed must be the SSZ-91 of pole pure phase to avoid a large amount of EUO phases of formation.When as seed, crystal seed Addition for silicon source weight in reaction mixture 0.5% to 5%.
By optimizing hexamethylene bromide/SiO2The concentration of ratio, control hydroxide concentration and minimum sodium is come minimum Change the formation of Magadiite and Kenyaite, because Magadiite and Kenyaite are laminar silicic acid composition of sodium.Following How embodiment changes the guidance that gelation condition minimizes the formation of EU-1 if providing.
Molecular sieve crystal once being formed, by standard mechanical separation techniques as filtered solid product and reaction mixture point It leaves.Crystal is washed, is then dried with the molecular sieve crystal of original sample after being synthesized.Drying steps can under atmospheric pressure or It carries out under vacuum.
Crystallization post processing
Molecular sieve uses as former state after can synthesizing, but will usually be heat-treated (calcining).Term " after synthesis as former state " refers to After crystallization, before SDA cations are removed form molecular sieve.SDA can be removed by heat treatment (such as calcining), excellent It is selected in oxidizing atmosphere (such as air, partial pressure of oxygen are more than the gas of 0kPa), is enough what those skilled in the art easily determined At a temperature of removing the SDA from molecular sieve.SDA can be also removed by ozonisation and photodissociation technology (for example, being enough from molecule In sieve under conditions of selective removal organic compound, the molecular sieve product containing SDA is exposed to the wave shorter than visible ray Long light or electromagnetic radiation), it describes in U.S. Patent No. 6,960,327.
Then, molecular sieve is forged in steam, air or inert gas at a temperature of about 200 DEG C~about 800 DEG C Burn and continue 1~48 hour or longer time.General it is desired that extraframework cation (such as Na is removed by ion exchange+) And it is replaced with the metal ion of hydrogen, ammonium or any desired.
In the case of the molecular sieve of formation is sieved for intermediate molecule, such as heteroatom lattice of technology after synthesis is used to replace Technology can obtain target molecule sieve.Hetero atom is removed from lattice using known technology such as acidleach, can also obtain target Molecular sieve (for example, silicate SSZ-91).
The molecular sieve prepared by method disclosed herein can be formed as a variety of physical behaviors.In general, the molecule Sieve can be powder, particle or mold compound form for example with being enough through 2 mesh (Taylor) sieve and to be retained in 400 mesh (safe Strangle) extrudate of the granularity of sieve.In the case of for example being extruded by using organic bond to shaping of catalyst, energy It is enough before the drying to squeeze out molecular sieve or the molecular sieve is dry or partially dried, then squeeze out.
Can by the molecular sieve with to being used in organic conversion processes temperature and other conditions have tolerance its His substance carries out compound.This basis material include active and inactive substance and synthesis or naturally-produced molecular sieve and Inorganic material such as clay, silica and metal oxide.It is disclosed in U.S. Patent No. No. 4,910,006 and No. 5,316,753 The example of this material and its occupation mode.
Then such as technology of dipping or ion exchange can be used, use one kind of the metal selected from periodic table 8-10 races Or various active metal further loads extrudate or particle, to enhance hydrogenating function.Such as U.S. Patent No. 4,094,821 Disclosed in, disposably by modified metal and one or more 8-10 races metals, dipping may be desired jointly.One In a embodiment, at least one active metal is selected from nickel, platinum, palladium and combinations thereof.After Metal Supported, carried metal squeezes Going out object or particle can calcine in air or inert gas at a temperature of 200 DEG C to 500 DEG C.In one embodiment, The extrudate of carried metal is calcined in air or inert gas at a temperature of 390 DEG C to 482 DEG C.
SSZ-9 can be used for various hydrocarbon conversion reactions, such as is hydrocracked, dewaxes, the alkane of isomerisation of olefin, aromatic compounds Base and isomerization etc..SSZ-91 also is used as being generally separated the adsorbent of purpose.
The characterization of molecular sieve
There is 40 to 200 SiO by molecular sieve prepared by method disclosed herein2/Al2O3Molar ratio (SAR).Pass through Inductively coupled plasma (ICP) elemental analysis determines SAR.In a sub- embodiment, SSZ-91 have 70 and 160 it Between SAR.In another sub- embodiment, SSZ-91 has the SAR between 80 and 140.
Such as by DIFFaX simulations and if Lobo and Koningsveld is in J.Am.Chem.Soc.2012,124, Measured described in 13222-13230, SSZ-91 materials by least 70% the whole ZSM-48 section bars material being present in product Polytype 6 form, wherein unordered to adjust by three kinds of different staggered floor probability.It should be noted that phrase " at least X% " Situation including other ZSM-48 polytypes are not present in structure, i.e. the material is 100% polytype 6.The structure of polytype 6 is such as (referring to J.Am.Chem.Soc.2002,124,13222-13230) described in Lobo and Koningsveld.In an embodiment In, SSZ-91 materials are made of the polytype 6 of at least 80% whole ZSM-48 section bars material being present in product.At another In embodiment, SSZ-91 materials are made of the polytype 6 of at least 90% whole ZSM-48 section bars material being present in product. 6 structure of polytype gives skeletal code * MRE by the structure committee of International Zeolite Association.
Molecular sieve SSZ-91 has the form for being characterized as polycrystalline aggregate, has about 100nm to 1.5 μm of diameter, often A aggregation includes the crystallite aggregate generally with 1 to 8 average aspect ratio.As it is used herein, term diameter is Refer to the shortest length in the short end of each crystallite checked.Compared with the ZSM-48 materials with high aspect ratio, SSZ-91 Show being hydrocracked for lower degree.In a sub- embodiment, average aspect ratio is between 1 and 5.In another height reality It applies in scheme, average aspect ratio is between 1 and 4.In another sub- embodiment, average aspect ratio is between 1 and 3.
The molecular sieve synthesized by method disclosed herein can be characterized by their XRD diagram.The powder X-ray RD of table 2 Spectral line represents the SSZ-91 of original sample after the synthesis prepared according to methods described herein.Due to the variation of lattice constant, specific sample The variation of molar ratio of skeleton type may lead to the minor change of diffraction pattern.In addition, sufficiently small crystal can influence peak Shape and intensity lead to apparent peak stretching.The minor change of diffraction pattern may also be by the organic compound used in preparation The variation of Si/Al molar ratios between variation and sample causes.Calcining can also lead to the minor change of XRD diagram.Although it deposits In these small disturbances, but basic lattice structure remains unchanged.
Table 2
The characteristic peak of the SSZ-91 of original sample after synthesis
(a)±0.20
(b)The powder xrd pattern provided is based on relative intensity scale, and wherein spectral line most strong in X ray picture is appointed as 100 Value：W=it is weak (>0 to≤20)；M=it is medium (>20 to≤40)；S=it is strong (>40 to≤60)；VS=it is very strong (>60 to≤ 100)
The spectral line of the figure X-ray diffractogram of table 3 represents the SSZ-91 after the calcining prepared according to methods described herein.
Table 3
The characteristic peak of SSZ-91 after calcining
(a)±0.20
(b)The powder xrd pattern provided is based on relative intensity scale, and wherein spectral line most strong in X ray picture is appointed as 100 Value：W=it is weak (>0 to≤20)；M=it is medium (>20 to≤40)；S=it is strong (>40 to≤60)；VS=it is very strong (>60 to≤ 100)
X-ray diffractogram of powder shown in this article is collected by standard technique.It radiates and is radiated for CuK α.From the relatively strong of peak Degree (being adjusted for background) reads peak heights and the position of the function as 2 θ (wherein θ is Bragg angle), and can calculate With the corresponding interplanar distance d of call wire.
Embodiment
Following illustrative embodiment is intended to be non-limiting.
Embodiment summary
The following examples show the three kinds of unique combination features (low aspect ratio, low EU-1 contents, the height that lack SSZ-91 Polytype 6 forms) in any ZSM-48 materials will show the catalytic performance gone on business.Following table 4 summarizes hereafter general The hydrotreating performance for the various embodiments stated.Compared with other three embodiments, only embodiment 8 (SSZ-91) is shown excellent Different performance, i.e., excellent selectivity and low gas yield.Remaining material performance tested in other three embodiments is gone on business Performance because each lack at least one of three unique combination features for defining SSZ-91.
Table 4
Comparative example 1
The synthesis of ZSM-48
Product in the present embodiment is to authorize Thomas F.Degnan and Ernest according on December 24th, 1991 Prepared by the introduction of the U.S. Patent No. 5,075,269 of W.Valyocsik (Mobil Oil Corp.), use is available Reagent.
76.51 grams of NaOH (50%), 846 grams of deionized waters, 124.51 grams of HI-SIL are added in into 1 gallon of autoclave liner 233 silica (PPG Industries) and 63 grams of hexamethylene bromide (" HMB, " Sigma Aldrich).In all solids After dissolving, 396 grams of aluminium stock solutions are added in, by dissolving 4.35 grams of Al2(SO4)3●18H2O and 63 gram of concentrated sulfuric acid arrives 733.52g it is prepared in deionized water.Finally, SSZ-91 crystal seeds of the 0.45g from embodiment 7 is added in.Mixture is stirred until It is even.Generated aluminosilicate gels have the composition of following molar ratio：
Table 5
Liner is transferred in 1 gallon of autoclave, was heated to 160 DEG C in 8 hours, and at autogenous pressures with The rate stirring of 150rpm.After 80 hours, filtration product is washed with deionized and dries.Obtained solid is by XRD determining ZSM-48 materials (Fig. 1).XRD shows that the amount of EU-1 in product is immeasurablel amount (EU-1 for being possibly less than 1%).SEM is shown The minute hand (Fig. 2) of the aggregation of ZSM-48 crystal, aspect ratio 7-12 are shown.
Comparative example 2 and 3
As described above, Lobo and Koningsveld papers describe them to by Chevron Corporation's The analysis for three kinds of ZSM-48 samples that Alexander doctors Kuperman provide.Each sample A, B and C in three samples It is prepared respectively using three kinds of different structure directing agents.Sample A is described as polytype 6 by Lobo and Koningsveld papers, will Sample B is described as defect polytype 6.The paper further describes the form (Fig. 3) of sample A, by a diameter of about 20nm and The needle crystals composition that length is about 0.5 μm.The form of sample B (Fig. 4) is long and narrow by 4-8 μm of diameter about 30nm and length Crystal composition.Although the material of doctor Kuperman is reported as the polytype 6 with high concentration, for the sample of sample A The aspect ratio (length/diameter) of feature be 25, for sample B sample characteristic aspect ratio between 133 and 266.
Embodiment 4-11
The synthesis of SSZ-91 with different EU-1 concentration in product
By by NaOH (50%), deionized water, 233 silica of HI-SIL (PPG Industries), bromination pregnancy Double ammoniums (Sigma Aldrich) add in autoclave liner to prepare each in embodiment 4 to 11.It is dissolved in all solids Afterwards, aluminium stock solution is added in, by dissolving 4.18 grams of Al2(SO4)3●18H2O and 45.58 gram of concentrated sulfuric acid to 540.6 grams go from It is prepared in sub- water.Mixture is stirred until uniformly.The following table 6 lists molar ratio and the heating time of aluminosilicate gels.
Table 6
Liner is transferred in autoclave, is heated to 160 DEG C within the time of 8 hours, and at autogenous pressures with The rate stirring of 150rpm.After the crystallization phase, filtration product is washed with deionized and dries.By XRD analysis obtained solid with Determine the content of EU-1 in product and product.Volume SiO2/Al2O3Molar ratio and EU-1 contents are listed in the table below in 7.
Table 7
Pass through the product of XRD and sem analysis from embodiment 1 and 4-11.The XRD diagram of embodiment 7 is shown in Figure 5, and It is the explanation for remaining embodiment 4-11 XRD diagram collected.
The SEM image of embodiment 7 and 8 is respectively displayed in Fig. 6 and 7, and is the SEM image of remaining embodiment 4-11 Explanation.The display SSZ-91 materials of Fig. 6 and 7 are made of polycrystalline aggregate, and each aggregation is made of crystallite, wherein each crystallite has There is the feature average aspect ratio less than 8.In contrast, the ZSM-48 materials of comparative example 1-3 (Fig. 2-4) contain minute hand and fiber shape State, the presence of the form show the catalytic performance of difference always.
The calcining of molecular sieve and ion exchange
By the product of original sample after the synthesis from comparative example 1 and embodiment 4-11 with 1 DEG C/min's under dry air atmosphere The rate of heat addition rises to 120 DEG C and is kept for 120 minutes, is then warming up to 540 DEG C and herein for the second time with the speed of 1 DEG C/min At a temperature of kept for 180 minutes, finally carrying out third time with the speed of 1 DEG C/min is warming up to 595 DEG C and keeps 180 at this temperature Minute is so as to be converted to na form.Finally, sample is cooled to 120 DEG C or lower.Then by each in these calcining samples According to being exchanged into ammonium form as described below.Sample quality ten will be dissolved completely in equal to the ammonium nitrate of the amount of sample quality to be exchanged In the deionized water of amount again.Then sample is added in ammonium nitrate solution, suspension is sealed in flask, and at 95 DEG C Baking oven in heated overnight.Flask from baking oven is taken out, sample is recycled by filtering immediately.Being repeated on the sample of recycling should Ammonium exchange process is washed to conductivity with a large amount of deionized waters and is less than 50 μ S/cm, finally 3 hours dry in 95 DEG C of baking oven.
Hydrotreating is tested
It is enterprising in the ammonium exchange sample from embodiment 1 and 4-11 using four ammino palladium (II) (0.5 weight %Pd) of nitric acid Row palladium ion exchanges.It is after ion exchange, sample is dry at 95 DEG C, 3 hours are then calcined in 482 DEG C of air with by nitre Sour four ammino palladiums (II) are converted into palladium oxide.
By 0.5 gram of each palladium from embodiment 11 exchange sample be loaded in it is 23 inches long × 0.25 inch outer diameter it is stainless The loading of the center of steel reaction tube, wherein corundum swims that (gross pressure is 1200psig using pre- hot feed on a catalyst；It flows downward Hydrogen rate is 1mL/min (being measured at 1 atmospheric pressure and 25 DEG C)；The liquid feed rate to flow downward is 160mL/ hours). All material restores 1 hour, every 30 points by online capillary gas chromatography (GC) first in the hydrogen of flowing in about 315 DEG C Clock analysis product is primary, the initial data of GC is collected by automatic data accquisition/processing system, and calculate hydrocarbon from initial data and turn Rate.
Catalyst is initially tested at 260 DEG C to determine the temperature range of next group of measurement.Bulk temperature range will provide Large-scale hexadecane conversion, maximum conversion rate are following and more than 96%.Five online GC are at least collected at each temperature Injection.Conversion ratio is defined as generating other products (including iso- nC16Isomers) hexadecane reacting dose.Yield is expressed as except n- C16The weight percent of product in addition, and including iso- C16As yield product.As a result it is listed in table 8.
Table 8
For the preferred material of the present invention, desired isomerisation selectivity is at least 85% under 96% conversion ratio.Isomery Change selectivity 96% conversion ratio under temperature between it is well balanced be vital for the present invention.Under 96% conversion ratio Desired temperature be less than 605 °F.Temperature under 96% conversion ratio is lower, more it is expected that catalyst still keeps at least 85% simultaneously Isomerisation selectivity.The collaboration that best catalytic performance depends under 96% conversion ratio between isomerisation selectivity and temperature is made With.A large amount of impurity leads to undesirable catalytic cracking, and adjoint high gas yield passes through increased C4 -Cracking level reflects In table 8.C needed for material of the present invention4 -Cracking is less than 2.0%.Note that selectivity is begun to decline when EU-1 is 6.82%, Because the increase of EU-1 concentration can promote catalytic cracking.
Polytype is distributed
Using DIFFaX, generation has the simulation XRD diagram of the ZSM-48 materials of the polytype 6 between 70% and 100%, and It is compared with the XRD diagram collected for the molecular sieve product from embodiment 8 and 11.Simulation and product X RD figure difference It is presented in this paper Fig. 8 and 9.The product that the comparison of product X RD figures and simulation drawing shows to synthesize in embodiment 8 and 11, which contains, to be more than 90% polytype 6.
Using DIFFaX, generation has the simulation XRD diagram of the ZSM-48 materials of the polytype 6 between 70% and 100%, and The XRD diagram that its molecular sieve product with comparative example 1 is collected is compared.Simulation and product X RD figures are presented in this paper Figure 10. Product X RD schemes the product that the comparison with simulation drawing shows to synthesize in comparative example 1 and contains 80% polytype 6.
The hexadecane hydrotreating carried out as described in above-described embodiment 4-11 to the material synthesized in comparative example 1 is tested.Come From the isomerisation selectivity of material display 78% under 96% conversion ratio at a temperature of 614 °F of comparative example 1.Such as the following table 9 institute Show, C4 -Cracking is 2.8%.It is only 80% 1 material of comparative example for 6 content of polytype as shown in upper table 7, in 96% conversion Isomerisation selectivity under rate is less than the isomerisation selectivity described in embodiment 4 to 10, even if comparative example 1 contains immeasurability Amount (<1%) EU-1.Although this show the material of comparative example 1 and embodiment 11 show SSZ-91 three kinds of features it is (low vertical It is horizontal than, low EU-1 contents, 6 content of high polytype) in two kinds, but lack third feature cause material difference catalytic performance.
Table 9
Embodiment 12-13
SSZ-91 is synthesized using replacement of silicon dioxide source
By by NaOH (50%), deionized water, CAB-O-SIL M-5 silica (Cabot Corporat ion) and Hexamethylene bromide (HMB) prepares the material of embodiment 12 added to autoclave liner.After all solids dissolving, add in anhydrous Riedel de Haen sodium aluminates.Finally, the SSZ-91 slurries of the similar slurry from embodiment 4 are added in.It is straight to stir mixture To uniform.Prepared aluminosilicate gels have the composition of following molar ratio：
Table 10
Liner is transferred in autoclave, is heated to 160 DEG C within the time of 8 hours, and at autogenous pressures with The rate stirring of 150rpm.After 48 hours, filtration product is washed with deionized and dries.Obtained solid is by XRD determining SSZ-91 simultaneously contains the EUO of 0.30 weight %.It was found that volume SiO2/Al2O3Molar ratio is about 102.
By by NaOH (50%), deionized water, 2327 colloidal silicon dioxide (40.3%SiO of commercially available NALCO2) and bromine Change hexamethonium C6 added to autoclave liner to prepare the material of embodiment 13.After all solids dissolving, dissolving in advance is added in Al in some water2(SO4)3●18H2O.Mixture is stirred until uniformly.Prepared aluminosilicate gels have following rub The composition of your ratio：
Table 11
Liner is transferred in autoclave, is heated to 160 DEG C within the time of 8 hours, and at autogenous pressures with The rate stirring of 150rpm.After 35 hours, filtration product is washed with deionized and dries.Obtained solid is by XRD determining SSZ-91 simultaneously contains the EU-1 of 3.16 weight %.It was found that volume SiO2/Al2O3Molar ratio is about 155.Pass through scanning electron microscopy Mirror analyzes the material of embodiment 13, and the SEM image from the analysis is shown in Figure 11.
Hydrotreating is tested
For the SSZ-91 materials synthesized in embodiment 12 and 13, palladium load is carried out as described in above for embodiment and is urged Change test.The result for being catalyzed test is as shown in table 12 below.The two examples prepared by changing raw materials are shown Diversity prepared by SSZ-91.Embodiment 12 shows another good example, under 96% at significantly lower temperature Desired isomerisation selectivity is 88%.Although embodiment 13 is pure phase, show poor catalytic performance, this be because The crystal habit of aspect ratio difference for crystal.
Table 12
Using DIFFaX, generation has the simulation XRD diagram of the ZSM-48 materials between 70% and 100% polytype 6, and will It is compared with the XRD diagram collected for the molecular sieve product from embodiment 13.Simulation and product X RD figures are in be shown in herein In Figure 12.SEM figures from the analysis are shown in Figure 11 A, and the comparison that product X RD schemes with simulation drawing shows to close in comparative example 1 Into product contain polytype 6 more than 90%.Although this show embodiment 13 material have necessary low EU-1 contents and Desired polytype distribution, but high aspect ratio leads to the catalytic performance of the difference of material.Embodiment 13 demonstrates again that the three of SSZ-91 The shortage of any one of a feature (low aspect ratio, low EU-1 contents, 6 content of high polytype) leads to the catalysis of the difference of material Performance.

Claims (14)

1. a kind of molecular sieve for belonging to ZSM-48 zeolites race, wherein the molecular sieve includes：
40 to 200 silica to the molar ratio of aluminium oxide,
6 and of polytype based on the whole ZSM-48 section bars material meters at least 70% being present in product
Other EUO type molecular sieve phases, amount are the 0-3.5% of all over products by weight；With
Wherein described molecular sieve has the shape for being characterized as the polycrystalline aggregate for including the overall crystallite with average aspect ratio 1 to 8 State.
2. molecular sieve according to claim 1, wherein the molecular sieve has substantially after its synthesis under intact form X-ray diffractogram as shown in the table：
(b)W=it is weak (>0 to≤20)；M=it is medium (>20 to≤40)；S=it is strong (>40 to≤60)；VS=it is very strong (>60 to≤ 100)。
3. molecular sieve according to claim 1 or 2, wherein the molecular sieve has 70 to 160 silica to aluminium oxide Molar ratio.
4. molecular sieve according to any one of claim 1 to 3, wherein the molecular sieve has 80 to 140 silica To the molar ratio of aluminium oxide.
5. according to the molecular sieve described in any one of claim 1-4, wherein the molecular sieve includes, based on being present in product Whole ZSM-48 section bars material meters at least 80% polytype 6.
6. molecular sieve according to any one of claim 1 to 5, wherein the molecular sieve includes 0.1 to 2 weight %'s EU-1。
7. the molecular sieve as described in any one of claim 1-6, wherein the crystallite totally has 1 to 5 average aspect ratio.
8. according to the molecular sieve described in any one of claim 1-7, wherein the molecular sieve includes being based on being present in product Whole ZSM-48 section bars material meters at least 90% polytype 6.
9. according to the molecular sieve described in any one of claim 1-8, wherein the crystallite totally has being averaged between 1 to 3 Aspect ratio.
10. a kind of method for the molecular sieve for preparing any one of claim 1-9, including preparing reaction mixture, the reaction Mixture contains at least one silicon source, at least one silicon source, the source of at least one element selected from periodic table the 1st and the 2nd race, hydrogen Oxygen radical ion, hexamethonium C6 cation and water；And the reaction mixture experience is made to be enough to form the knot of the molecular sieve crystal Crystal bar part.
11. according to the method described in claim 10, wherein described molecular sieve is prepared by reaction mixture, the reaction mixture Following substance is included according to the molar ratio：
Wherein M is selected from periodic table the 1st and the element of 2 races；And Q is hexamethonium C6 cation.
12. according to the method described in claim 10, wherein described molecular sieve is prepared by reaction mixture, the reaction mixture Following substance is included according to the molar ratio：
Wherein M is selected from periodic table the 1st and the element of 2 races；And Q is hexamethonium C6 cation.
13. a kind of method for hydrocarbon conversion, including making hydrocarbonaceous feed at hydrocarbon conversion conditions and comprising according to claim 1-9 Any one of molecular sieve catalyst contact.
14. a kind of purposes of molecular sieve as claimed in one of claims 1-9, for converting hydrocarbon at hydrocarbon conversion conditions.
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